CN105319171B - The detection device and detection method of nitrite or nitrate content - Google Patents
The detection device and detection method of nitrite or nitrate content Download PDFInfo
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- CN105319171B CN105319171B CN201510790255.7A CN201510790255A CN105319171B CN 105319171 B CN105319171 B CN 105319171B CN 201510790255 A CN201510790255 A CN 201510790255A CN 105319171 B CN105319171 B CN 105319171B
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Abstract
The invention discloses the detection devices and detection method of a kind of nitrite or nitrate content, including peristaltic pump, floating cuvette, light source, optical receiver, cadmium circle and 7 three-way magnetic valves, pass through control peristaltic pump and selectively sample introduction, circulation, colour developing, reduction and the waste discharge of multichannel three-way magnetic valve, so as to shorten the flow path of detection device, integrated level is high, it is small in size, it is suitble to on-line analysis.It is designed by using circulation, reaction efficiency greatly improves, and the reaction product concentration in entire loop is uniform, can repeatedly measure and be averaged, and collimation and stability greatly improve.In addition, the present invention is used as reduction component using cadmium circle, allows sample solution to be measured to flow through in cadmium circle according to certain speed, both improved the work that reduction efficiency in turn avoids filling repeatedly, it is easy to operate, while avoiding the use of poisonous and harmful reagent.
Description
Technical field
The invention belongs to sewater chemistry analysis technical fields, specifically, be related to it is a kind of for detecting the Asia in seawater
The device and method of nitrate and nitrate content.
Background technique
Nitrite, nitrate are widely present in ocean water body, are one of the important parameters of marine eco-environment monitoring.
Currently, the nitrite and nitrate measurement in seawater are mainly according to marine monitoring specification (GB 17378-2007), using base
In spot sampling-laboratory method of research vessel.This method there are real-times poor, testing sample solution vulnerable to pollution, waste
The disadvantages of manpower and material resources.In recent years, on-line determination device and method become one of the research hotspot of marine field.
Currently, the main measuring methods of nitrite in seawater, nitrate are spectrophotometry, react aobvious using Griess
It is quantitative determined after color.Wherein, nitrite can directly be reacted with color developing agent and be detected；Nitrate then needs to be reduced into
It is measured again after nitrite.Restoring the common method of nitrate is Cadmium reduction column, i.e., under conditions of pH=8, nitric acid
Salt is reduced into after nitrite by copper facing cadmium grain and is measured again.Although this method reduction efficiency is higher, with access times
Increase, it may appear that the problem of reduction efficiency declines needs to reactivate cadmium grain, refills dress column, operates than relatively time-consuming.
The existing on-line checking to nitrite in seawater, nitrate mainly relies on Flow Injection Technique, measures immediately
The absorbance of colour developing product.But test point at this time is not necessarily the reaction highest point of completeness, that there are collimations is poor,
The problems such as stability is poor, reaction is incomplete.Moreover, in reaction flow path, it is easy to generate bubble, largely will affect
The accuracy of testing result.
Summary of the invention
The device that the purpose of the present invention is to provide a kind of for detecting nitrite and nitrate content in seawater and
Method improves the stability and accuracy of testing result with streamline operation.
In order to solve the above technical problems, the present invention is achieved by the following scheme:
A kind of detection device of nitrite or nitrate content, comprising: the first three-way magnetic valve, normal open entrance are used for
Sample solution to be detected is received, normally closed entrance is for receiving distilled water；Second three-way magnetic valve, normal open entrance connection the
The outlet of one three-way magnetic valve；Third three-way magnetic valve, normal open entrance be connected to the second three-way magnetic valve outlet, it is normally closed enter
Mouth is for receiving buffer solution；4th three-way magnetic valve, normal open entrance be connected to third three-way magnetic valve outlet, it is normally closed enter
Mouth is connected to the outlet of the third three-way magnetic valve by cadmium circle；5th three-way magnetic valve, normal open entrance are connected to the 4th threeway
The outlet of solenoid valve, normally closed entrance is for receiving the first color developing agent；6th three-way magnetic valve, normal open entrance connection the five or three
The outlet of three-way electromagnetic valve, normally closed entrance is for receiving the second color developing agent；Peristaltic pump, entrance are connected to the 6th three-way magnetic valve
Outlet；Floating cuvette, entrance are connected to the outlet of peristaltic pump, optical entrance are provided on the floating cuvette and light goes out
Loophole；Light source, the optical entrance of floating cuvette described in face, the liquid in transmitting light irradiation floating cuvette；
Optical receiver, the optical emission exit of floating cuvette described in face receive the light projected by optical emission exit, and convert
At electric signal, output to signal processing system；7th three-way magnetic valve, entrance are connected to the outlet of floating cuvette, normal open
Outlet is for being discharged waste liquid, the normally closed entrance of normally closed the second three-way magnetic valve of outlet.
Preferably, the floating cuvette is made of quartz, and internal is that cuboid or column type cavity, outside are enclosed with
Black polyethylene is protected from light shell；The outlet of the floating cuvette is located at the top of floating cuvette；The optical entrance and light
Exit portal sets up separately on the left side wall and right side wall of floating cuvette, and is located on same axis.
Preferably, the light source is the LED light that center wavelength is 530nm；The optical receiver is photodiode.
Preferably, the cadmium circle is coated with PVC protective layer outside the cadmium pipe preferably by cadmium pipe ring around forming, with
Completely cut off air and water.
It further, further include a threeway in the detection device, the threeway is T-type or Y type, entrance connection
The outlet of the third three-way magnetic valve, the normal open entrance of one connection the 4th three-way magnetic valve in two outlet are another
A normally closed entrance that the 4th three-way magnetic valve is connected to by the cadmium circle.
It further include a fluid branch manifold in the detection device in order to facilitate the entirety assembly of component each in detection device
Valve plate is carved with fluid channel in the inside of the fluid branch manifold valve plate, by the peristaltic pump, floating cuvette, light source, photoelectricity
Diode, cadmium circle and all three-way magnetic valves are mounted on the fluid branch manifold valve plate, are led between each road three-way magnetic valve
Cross the fluid channel connection.
Based on the detection device of above-mentioned nitrite or nitrate content, the present invention also provides a kind of content of nitrite
Detection method, comprising the following steps:
A, peristaltic pump, light source and the first three-way magnetic valve are opened, the flow path of detection device described in distilled water flushing is pumped into, and
Incident intensity I is acquired by optical receiver0；
B, the first three-way magnetic valve described in closing, is exported to switch to and is connected to its normal open entrance, is pumped into known dense
The nitrite standard solution of degree；
C, the 5th three-way magnetic valve is opened, after being pumped into a certain amount of first color developing agent, closes the 5th three-way magnetic valve；
The 6th three-way magnetic valve is opened, after being pumped into a certain amount of second color developing agent, closes the 6th three-way magnetic valve；
D, it opens the second three-way magnetic valve and the 7th three-way magnetic valve forms closed loop flow path, keep the nitrite standard molten
Liquid and the first color developing agent and the second color developing agent are formed by mixed liquor abundant reaction solution in circulation；
E, the mixed liquor in the light source irradiation floating cuvette is opened；
F, pass through the optical receiver acquisition of transmission light intensity I1, by formula A=-lg (I1/I0) calculate the standard solution
The absorbance of middle nitrite；
G, second three-way magnetic valve and the 7th three-way magnetic valve are closed, waste liquid is discharged；
H, the nitrite standard solution for replacing various concentration, repeats the step a-g, draws out nitrite
Absorbance-concentration relationship curve；
I, nitrite standard solution is substituted for sample solution to be measured, step a-g is repeated, according to calculated
The absorbance of nitrite in sample solution and the absorbance of the nitrite-concentration relationship curve, obtain the sample
The content CNO of product nitrite in solution2 _-N。
In order to improve the accuracy of testing result, preferably when carrying out illumination detection to the sample solution, multiple groups are acquired
Transmitted light intensity calculates multiple groups content of nitrite value, is then averaging to the multiple groups content of nitrite value, as most
Whole measurement result.
Based on the detection device of above-mentioned nitrite or nitrate content, the present invention also provides a kind of inspections of nitrate content
Survey method, comprising the following steps:
A, peristaltic pump, light source and the first three-way magnetic valve are opened, the flow path of detection device described in distilled water flushing is pumped into, and
Incident intensity I is acquired by optical receiver0；
B, the first three-way magnetic valve described in closing, is exported to switch to and is connected to its normal open entrance, is pumped into known dense
The nitrite standard solution of degree；
C, the 5th three-way magnetic valve is opened, after being pumped into a certain amount of first color developing agent, closes the 5th three-way magnetic valve；
The 6th three-way magnetic valve is opened, after being pumped into a certain amount of second color developing agent, closes the 6th three-way magnetic valve；
D, it opens the second three-way magnetic valve and the 7th three-way magnetic valve forms closed loop flow path, keep the nitrite standard molten
Liquid and the first color developing agent and the second color developing agent are formed by mixed liquor abundant reaction solution in circulation；
E, the mixed liquor in the light source irradiation floating cuvette is opened；
F, pass through the optical receiver acquisition of transmission light intensity I1, by formula A=-lg (I1/I0) calculate the standard solution
The absorbance of middle nitrite；
G, second three-way magnetic valve and the 7th three-way magnetic valve are closed, waste liquid is discharged；
H, the nitrite standard solution for replacing various concentration, repeats the step a-g, draws out nitrite
Absorbance-concentration relationship curve；
I, nitrite standard solution is substituted for sample solution to be measured, step a-g is repeated, according to calculated
The absorbance of nitrite in sample solution and the absorbance of the nitrite-concentration relationship curve, obtain the sample
The content CNO of product nitrite in solution2 _-N；
J, absorbance-concentration relationship curve of nitrate is drawn, comprising the following steps:
(1) peristaltic pump, light source and the first three-way magnetic valve are opened, the flow path of detection device described in distilled water flushing is pumped into,
And incident intensity I is acquired by optical receiver0'；
(2) close first three-way magnetic valve, export to switch to and be connected to its normal open entrance, be pumped into known to it is dense
The nitrate standard solution of degree；
(3) third three-way magnetic valve is opened, a certain amount of buffer solution is pumped into, is then turned on the second three-way magnetic valve and the
Seven three-way magnetic valves form circulation around circuit, and buffer solution and nitrate standard solution is made to be thoroughly mixed to form uniform solution；
(4) the 4th three-way magnetic valve is opened, so that the nitrate standard solution that buffer solution is added is flowed through cadmium circle and carries out repeatedly
Reduction, by the nitrate reduction in the standard solution at nitrite；
(5) the 5th three-way magnetic valve is opened, after being pumped into a certain amount of first color developing agent, closes the 5th threeway electromagnetism
Valve；The 6th three-way magnetic valve is opened, after being pumped into a certain amount of second color developing agent, closes the 6th three-way magnetic valve；
(6) the second three-way magnetic valve and the 7th three-way magnetic valve are opened and forms closed loop flow path, make the uniform solution and the
One color developing agent and the second color developing agent are formed by mixed liquor abundant reaction solution in circulation；
(7) mixed liquor in the light source irradiation floating cuvette is opened；
(8) pass through the optical receiver acquisition of transmission light intensity I1', by formula A=-lg (I1’/I0') calculate reduction after
The absorbance of nitrite in standard solution；
(9) second three-way magnetic valve and the 7th three-way magnetic valve are closed, waste liquid is discharged；
(10) the nitrate standard solution for replacing various concentration, repeats step (1)-(9), obtains multiple groups nitrite
Absorbance and nitrate concentration corresponding relationship, absorbance-concentration relationship curve of nitrate is drawn out with this；
K, nitrate standard solution is substituted for the sample solution to be measured, repeats the step (1)-(9), counted
The absorbance of nitrite in sample solution after calculating reduction, it is then bent using the absorbance of the nitrate-concentration relationship
Line obtains the content summation CNO of NO3-N and NO2-N in the sample solution3 _-N'；
L, the nitrate content CNO in the sample solution is calculated3 _- N=CNO3 _-N’-CNO2 _-N。
In order to improve the accuracy of testing result, preferably when carrying out illumination detection to the sample solution after reduction, acquisition
Multiple groups transmitted light intensity calculates multiple groups nitrate content value, is then averaging to the multiple groups nitrate content value, as most
Whole measurement result.
Preferably, the buffer solution is preferably ammonium chloride buffer solution or imidazole buffer solution, wherein is pumped into institute
The volume ratio for stating the buffer solution and sample solution in detection device is 1:1；First color developing agent is preferably p-aminophenyl sulphur
Amide-aqueous hydrochloric acid solution, wherein the concentration of P-aminobenzene-sulfonamide is 5-30g/L, and the concentration of hydrochloric acid is 1-2mol/L, and is pumped
Enter to the first color developing agent and sample solution in the detection device volume ratio be 1:50；The second color developing agent NED is preferred
For hydrochloride naphthodiamide aqueous solution, wherein the concentration of hydrochloride naphthodiamide is 1.0-5.0g/L, and is pumped into the detection device
In the second color developing agent and sample solution volume ratio be 1:50.
After cadmium circle is used for multiple times, reduction efficiency can decline to a great extent, and need to put into again after activating it
It uses.For this purpose, described in the present invention activated again when the reduction efficiency of the cadmium circle drops to 90% or less, using following steps
Cadmium circle: open the peristaltic pump, third three-way magnetic valve and the 4th three-way magnetic valve, be pumped into the hydrochloric acid of 2mol/L, and continue 1
Minute；It is then pumped into copper activating fluid, and continues 2 minutes；It is pumped into the hydrochloric acid of 2mol/L again, and continues 5 minutes；Finally, being pumped into institute
The buffer solution stated, the activation of cadmium circle.
Compared with prior art, the advantages and positive effects of the present invention are:
1, detection device of the invention utilizes peristaltic pump and multichannel three-way magnetic valve selectivity sample introduction, circulation, colour developing, reduction
And waste discharge, the flow path of detection device is shortened, integrated level is high, and it is small in size, it is suitble to on-line analysis；
2, detection device of the invention allows sample solution to be measured in cadmium circle according to one using cadmium circle as reduction component
Fixed speed flows through, and has both improved the work that reduction efficiency in turn avoids filling repeatedly, as long as the first time using being cleaned and swashed
It is living, it is not necessarily to remove when activating again, can be completed in flow path, it is easy to operate, while avoiding poisonous and harmful reagent
It uses；
3, detection device of the invention is designed using circulation, and reaction efficiency greatly improves, and the reaction in entire loop generates
Object concentration is uniform, can repeatedly measure and be averaged, and collimation and stability greatly improve.
4, the column flow cuvette that detection device of the invention uses liquid to flow from the bottom up, the mistake for flowing liquid
The bubble generated in journey all concentrates on the top of test point, does not form interference to testing result, and testing result is stablized, collimation
It is high.
After the detailed description of embodiment of the present invention is read in conjunction with the figure, the other features and advantages of the invention will become more
Add clear.
Detailed description of the invention
Fig. 1 is a kind of whole knot of embodiment of the detection device of nitrite or nitrate content proposed by the invention
Structure schematic diagram；
Fig. 2 is absorbance-concentration relationship curve generation method flow chart of nitrite；
Fig. 3 is a kind of flow chart of embodiment of the content of nitrite detection method in sample solution；
Fig. 4 is absorbance-concentration relationship curve generation method flow chart of nitrate；
Fig. 5 is a kind of flow chart of embodiment of the nitrate content detection method in sample solution.
Specific embodiment
A specific embodiment of the invention is described in detail with reference to the accompanying drawing.
The detection device of the present embodiment is mainly for detection of the nitrite and/or nitrate in the sample solutions such as seawater
Content, including peristaltic pump P, floating cuvette F, light source led, optical receiver D, cadmium circle C and seven three-way magnetic valve V1-V7 etc. are main
Component part is wanted, as shown in Figure 1.
Installation for the ease of component each in detection device is fixed, and the present embodiment is preferably arranged one in the detection device
Fluid branch manifold valve plate (not shown), it is preferred to use organic glass is made, to prevent the erosion of the solution such as acid, alkali, with high salt.
It is etched with a plurality of fluid channel in the inside of the fluid branch manifold valve plate, these fluid channels are used to as a part of flow path
It is connected to three-way magnetic valve, to shorten the length of flow path, reduces interface and leak source.The present embodiment is on the fluid branch manifold valve plate
Threaded hole and drainage through-hole are offered, the threaded hole is used for other portions by the way of being threadedly coupled in fixed test device
Part, such as three-way magnetic valve V1-V7, peristaltic pump P, floating cuvette F, light source led, optical receiver D, cadmium circle C and fluid are defeated
Send pipe etc.；The drainage through-hole is used to be connected to the fluid channel inside three-way magnetic valve and valve plate.
7 three-way magnetic valve V1-V7 are two-position three way, and an aperture on first is to be connected in flow path always
On, it can be used as outlet, can also be used as entrance；There are two apertures on second, and one is normal open mouth, the other is normally closed
Mouthful, the two apertures must be used as entrance or outlet simultaneously.For two apertures on second, defines described three and be powered
Magnet valve V1-V7 is in the aperture of connected state with the aperture on first when powering off closing as on normal open mouth, with first
The aperture that aperture is in state of isolation is normally closed port.When three-way magnetic valve V1-V7 is powered and opens, the normal open mouth and first
On aperture isolation, the normally closed port is connected to the aperture on first.Change the on-off electricity condition of three-way magnetic valve V1-V7,
The flow direction and selectivity that can control fluid flow into.In the present embodiment, the three-way magnetic valve V1-V7 is preferably used
PEEK material is made, to prevent the erosion of the solution such as acid, alkali, with high salt.
In the present embodiment, the aperture on first will be on six of them three-way magnetic valve V1-V6 as outlet, place
In two apertures on second as entrance；Using the aperture on first in the 7th three-way magnetic valve V7 as entrance,
Two apertures on two are as outlet.
Below with reference to Fig. 1, the specific connection relationship between all parts in the detection device is described in detail.
As shown in Figure 1, the present embodiment by the normal open entrance of the first three-way magnetic valve V1 by fluid delivery tube and contain to
The vessel of sample solution are connected to, for receiving sample solution to be measured.By the normally closed entrance of the first three-way magnetic valve V1 via
Fluid delivery tube is connected to distilled water DIW, for introduction to distilled water DIW.By the outlet of a three-way magnetic valve V1 through the fluid
The fluid channel etched inside branch manifold valve plate is connected to the normal open entrance of the second three-way magnetic valve V2.The fluid delivery tube is preferred
The polyfluortetraethylene pipe or silicone tube that outer diameter is 0.5-2mm for 1-4mm, internal diameter are used, quickly flows requirement meeting liquid
While, the corrosion of the solution such as strong acid, highly basic, with high salt can be resistant to.For the second three-way magnetic valve V2, by its it is normally closed enter
Mouthful pass through the normally closed of the fluid channel that etches inside fluid branch manifold valve plate or fluid delivery tube and the 7th three-way magnetic valve V7
Outlet forms closed loop.The stream that the outlet of second three-way magnetic valve V2 is passed through into etching inside fluid branch manifold valve plate
Body channel is connected to the normal open entrance of third three-way magnetic valve V3.The normally closed entrance of third three-way magnetic valve V3 passes through fluid conveying
Pipe is connected to buffer solution BUF, for buffer solution BUF to be introduced into flow path.The outlet of third three-way magnetic valve V3 is led to
It crosses the fluid channel etched inside fluid branch manifold valve plate or fluid delivery tube is connected to the entrance of a threeway T, the threeway T
It can be T-type threeway, be also possible to Y-type three way type, by one of outlet of threeway T through etching inside fluid branch manifold valve plate
Fluid channel or fluid delivery tube are connected to the normal open entrance of the 4th three-way magnetic valve V4, another by threeway T exports
It is connected to through fluid delivery tube with the entrance of cadmium circle C.The cadmium circle C can be by cadmium pipe ring around forming, an entrance, one outlet,
It can play the role of mixing while restoring the nitrate in sample solution.In the present embodiment, the internal diameter of the cadmium pipe
Can be between 1.0-2.0mm, outer diameter can be between 1.5-5.0mm, and circling ring number is preferably between 3-20 circle, to meet nitre
The reduction requirement of hydrochlorate.One layer of PVC protective layer is preferably coated in the outside of the cadmium pipe, to completely cut off air and water.By cadmium circle C's
Outlet is connected to by fluid delivery tube with the normally closed entrance of the 4th three-way magnetic valve V4, and the outlet of the 4th three-way magnetic valve V4 passes through
The fluid channel etched inside fluid branch manifold valve plate is connected to the normal open entrance of the 5th three-way magnetic valve V5.5th threeway
The normally closed entrance of solenoid valve V5 is connected to the first color developing agent SAA by fluid delivery tube, for the first color developing agent SAA to be introduced into
In flow path.Fluid channel and the six or three by the outlet of the 5th three-way magnetic valve V5 through being etched inside fluid branch manifold valve plate
The normal open entrance of three-way electromagnetic valve V6 is connected to, and the normally closed entrance of the 6th three-way magnetic valve V6 passes through the second colour developing of fluid delivery tube connection
Agent NED, for the second color developing agent NED to be introduced into flow path.The outlet of the 6th three-way magnetic valve V6 is passed through into fluid
Delivery pipe is connected to the entrance of peristaltic pump P, and the outlet of the peristaltic pump P passes through the entrance of fluid delivery tube and floating cuvette F
Connection.In the present embodiment, the peristaltic pump P preferably uses 6 rotor pulse pumps, and pump discharge is between 0.4~24ml/min.Institute
It states floating cuvette F to be preferably made of quartz material, internal is cuboid or column type cavity, and it is poly- that outside is enclosed with black
Ethylene is protected from light shell.In the opposite two side walls of floating cuvette F, such as on left side wall and right side wall, two are offered respectively
A opposite window, using as optical entrance and optical emission exit.The light path for designing the floating cuvette F is 1-5cm, width is
10-25mm, height 20-50mm, window width are 1-10mm, high 2-20mm.The entrance and exit of floating cuvette F is arranged at
The top of cavity, so that fluid after filling entire floating cuvette F, could be flowed out from outlet.Due to what is generated in liquid
Bubble coalescence will not generate interference to incident light at the top of cavity, therefore can prevent bubble and cause to testing result
Influence, improve the accuracy of testing result.The outlet of floating cuvette F is passed through into fluid delivery tube and the 7th three-way magnetic valve
The entrance of V7 is connected to, and the normal open of the 7th three-way magnetic valve V7 exports connecting fluid delivery pipe, for waste liquid W to be discharged；7th threeway
The normally closed outlet of solenoid valve V7 is connected to the normally closed entrance of the second three-way magnetic valve V2, to form closed loop.
In the present embodiment, it is contemplated that the extinction characteristic of nitrite, the light source preferably use central wavelength for 530nm
LED light irradiate sample solution to be measured.Specifically, the light of the light-emitting surface face floating cuvette F of light source led is incident
Mouthful, it is incident by fiber optic conduction incident light after being the light line focus of 530nm, coupling by the central wavelength that light source led issues
Mouthful, and by after the liquid absorption in floating cuvette F, transmitted through optical emission exit, acquired by optical receiver D and convert out with
The corresponding electric signal of the light intensity received is sent to signal processing system PC and is calculated, to generate the extinction of liquid
Degree.In the present embodiment, the optical receiver D preferably uses the acquisition and conversion of photodiode progress light, at signal
Reason system PC calculate generate testing sample solution absorbance value and standard nitrite absorbance-concentration relationship curve into
Row comparison, can obtain the concentration of nitrite in sample solution.
Controller can be set in the detection device of the present embodiment, to the peristaltic pump P, light source led, optical receiver D
Opening and closing control is carried out with three-way magnetic valve V1-V7.
Using detection device shown in FIG. 1, by the unlatching for controlling peristaltic pump P and three-way magnetic valve V1, V2, V5, V6, V7
And closing, it is anti-to control sample solution S, the first color developing agent SAA, the Loading sequence of the second color developing agent NED, sample volume and circulation
Between seasonable, so as to realize the measurement to content of nitrite in sample to be tested solution S.For nitrate in sample solution S
The measurement of content needs first to determine the content of nitrite according to above-mentioned control method, is then kept by control peristaltic pump P
The flowing of liquid, and control three-way magnetic valve V1 and be pumped into sample solution S to be measured again, three-way magnetic valve V3 and V4 are controlled later
It opens to realize being pumped into for buffer solution BUF, and sample solution S to be measured is restored by cadmium circle C flow path, sample is molten
After nitrate reduction in liquid S is at nitrite, opened by control three-way magnetic valve V5 and V6 to realize the first color developing agent SAA
With being sequentially added for the second color developing agent NED, then controls three-way magnetic valve V2 and V7 and open to form circulation, to realize reduction reaction
With being repeatedly effectively performed for chromogenic reaction.The survey of content of nitrite is carried out to the sample solution S after reduction and chromogenic reaction
Fixed, calculated content of nitrite is the summation of nitrite and nitrate content in sample solution S at this time.Therefore, it incite somebody to action this
Calculated content of nitrite before secondary calculated content of nitrite subtracts, can be obtained nitrate in sample solution S
Content.Finally, being closed by control three-way magnetic valve V2 and V7, to disconnect circulation, so that waste liquid W is discharged, surveyed for next time
Surely it is ready.
Below with reference to detection device shown in FIG. 1, the specific detection method of content of nitrite in sample solution S is carried out
It is set forth.
Firstly, absorbance-concentration relationship curve of nitrite is drawn using the nitrite standard solution of various concentration,
As shown in Figure 2, comprising the following steps:
S201, peristaltic pump P, light source led and the first three-way magnetic valve V1 are opened, is pumped into distilled water DIW and rinses detection device
Flow path.
S202, the light transmitted by floating cuvette F is received by photodiode D, and is converted into electric signal
After export to signal processing system PC.After the signal processing system PC signal stabilization waiting received, current collected light is recorded
Line intensity is denoted as incident intensity I0。
S203, the first three-way magnetic valve V1 is closed；Close light source led；Close peristaltic pump P.
S204, peristaltic pump P and light source led are opened, is pumped into the nitrite standard solution of a certain amount of known concentration, makes institute
It states standard solution and is full of the flow path that detection device is currently connected to.
S205, the 5th three-way magnetic valve V5 is opened, after being pumped into a certain amount of first color developing agent SAA, closes the five or three and be powered
Magnet valve V5；
In the present embodiment, the first color developing agent SAA is preferably P-aminobenzene-sulfonamide-aqueous hydrochloric acid solution, wherein right
The concentration of aminobenzene sulfonamide is 5-30g/L, and the concentration of hydrochloric acid is 1-2mol/L, and first be pumped into the detection device
The volume ratio of color developing agent SAA and sample solution S is preferably 1:50.
As a kind of preferred embodiment of the present embodiment, the first color developing agent SAA is preferably formulated using following methods:
The P-aminobenzene-sulfonamide of 10.0g is dissolved in the distilled water of 250mL, places 5 minutes, adds the dense salt of 75mL
Acid uses water constant volume to 500mL after cooling, and the concentration for obtaining P-aminobenzene-sulfonamide is 20.0g/L, the concentration of hydrochloric acid is
The solution of 1.8mol/L forms the first color developing agent SAA.
S206, the 6th three-way magnetic valve V6 is opened, after being pumped into a certain amount of second color developing agent NED, closes the six or three and be powered
Magnet valve V6；
In the present embodiment, the second color developing agent NED is preferably hydrochloride naphthodiamide aqueous solution, wherein hydrochloric acid naphthalene second
The concentration of diamines is 1.0-5.0g/L, and the volume ratio for the second color developing agent and sample solution being pumped into the detection device is excellent
It is selected as 1:50.
As a kind of preferred embodiment of the present embodiment, the second color developing agent NED is preferably formulated using following methods:
It weighs 1.5 grams of hydrochloride naphthodiamide to be dissolved in the distilled water of 500mL, obtains the hydrochloric acid naphthalene second that concentration is 3.0g/L
Two amine aqueous solutions form the second color developing agent NED.
S207, the second three-way magnetic valve V2 and the 7th three-way magnetic valve V7 is successively opened, forms circulation around circuit, makes to be mixed with
The standard solution of first color developing agent SAA and the second color developing agent NED sufficiently react in circulation, develop the color, and make anti-in entire loop
It answers liquid concentration uniform, forms uniform solution.
S208, the uniform solution in floating cuvette F is irradiated by light source led, and pass through photodiode D acquisition of transmission
Light out, and after being converted into electric signal, output to signal processing system PC obtains transmitted light intensity I1。
S209, the second three-way magnetic valve V2 and the 7th three-way magnetic valve V7 is successively closed, disconnects circulation, waste liquid W is discharged.
S210, light source led is closed；Close peristaltic pump P.
S211, formula A=-lg (I is utilized1/I0) absorbance that calculates nitrite in standard solution, obtain one group of Asia
Corresponding relationship between the concentration and absorbance of nitrate.
The nitrite standard solution of S212, a variety of various concentrations of selection, repeat step S201-S211, obtain more
Corresponding relationship between the concentration and absorbance of group nitrite；According to the concentration of the multiple groups nitrite of acquisition and absorbance it
Between corresponding relationship, absorbance-concentration relationship curve of nitrite is drawn out, for nitrite in subsequent sample solution S
The measurement of content.
Secondly, using absorbance-concentration relationship curve of nitrite, to the nitrite in sample solution S to be measured
Content is measured, as shown in Figure 3, comprising the following steps:
S301, peristaltic pump P, light source led and the first three-way magnetic valve V1 are opened, is pumped into distilled water DIW and rinses detection device
Flow path.
S302, the light transmitted by floating cuvette F is received by photodiode D, and is converted into electric signal
After export to signal processing system PC.After the signal processing system PC signal stabilization waiting received, current collected light is recorded
Line intensity is denoted as incident intensity I01。
S303, the first three-way magnetic valve V1 is closed；Close light source led；Close peristaltic pump P.
S304, peristaltic pump P and light source led are opened, is pumped into a certain amount of testing sample solution S；
In the present embodiment, the amount of being pumped into of the sample solution S, which is subject to, is full of the flow path that detection device is currently connected to, with
Reduce the generation of bubble to the greatest extent.
In the present embodiment, why to prevent from generating bubble in flow path as far as possible, be because bubble can generate in a liquid
Interval causes sample solution S reaction incomplete.Illumination test, the extinction measured are carried out to incomplete sample solution S is reacted
Degree can there are a degree of differences with true value, then lead to the content of the nitrite finally calculated and nitrate not
Accurately.Therefore, when there are when bubble, will lead to measure unstable problem in sample solution S.
S305, the 5th three-way magnetic valve V5 is opened, after being pumped into a certain amount of first color developing agent SAA, closes the five or three and be powered
Magnet valve V5.
S306, the 6th three-way magnetic valve V6 is opened, after being pumped into a certain amount of second color developing agent NED, closes the six or three and be powered
Magnet valve V6.
S307, the second three-way magnetic valve V2 and the 7th three-way magnetic valve V7 is successively opened, forms circulation around circuit, makes to be mixed with
The sample solution S of first color developing agent SAA and the second color developing agent NED sufficiently react in circulation, develop the color, and make anti-in entire loop
It answers liquid concentration uniform, forms uniform solution.
S308, the uniform solution in floating cuvette F is irradiated by light source led, and pass through photodiode D acquisition of transmission
Light out, and after being converted into electric signal, output to signal processing system PC obtains transmitted light intensity I11。
S309, the second three-way magnetic valve V2 and the 7th three-way magnetic valve V7 is successively closed, disconnects circulation, waste liquid W is discharged.
S310, light source led is closed；Close peristaltic pump P.
S311, formula A=-lg (I is utilized11/I01) absorbance that calculates nitrite in sample solution S, according to meter
The absorbance of calculating and absorbance-concentration relationship curve of nitrite, can be obtained nitrite in the sample solution S
Content, be denoted as CNO2 _-N。
The measurement to content of nitrite in sample to be tested solution S is completed as a result,.
In the detection process, transmitted light intensity several times can be acquired more, calculate the content value of multiple nitrite, it is then right
Repeated detection result averaged, as the final detection result of content of nitrite in sample solution S, to improve detection knot
The accuracy of fruit.
Below with reference to detection device shown in FIG. 1, the specific detection method of nitrate content in sample solution S is carried out detailed
Carefully illustrate.
Detection to nitrate content in sample solution S, it is necessary first to complete to content of nitrite in sample solution S
Measurement, that is, be first carried out abovementioned steps S201-S212 and S301-S311, detect the nitrite in sample solution S to be measured
Content.
Secondly, drawing out absorbance-concentration relationship curve of nitrate using the nitrate standard solution of various concentration, such as
Shown in Fig. 4, comprising the following steps:
S401, peristaltic pump P, light source led and the first three-way magnetic valve V1 are opened, is pumped into distilled water DIW and rinses detection device
Flow path.The light transmitted by floating cuvette F is received by photodiode D, is received to signal processing system PC
To after stable signal, current collected light intensity is recorded, incident intensity I is denoted as0'.Close the first three-way magnetic valve V1,
Light source led and peristaltic pump P.
S402, peristaltic pump P and light source led are opened, is pumped into the nitrate standard solution of known concentration, and be full of detection device
The flow path being currently connected to.
S403, third three-way magnetic valve V3 is opened, after being pumped into a certain amount of buffer solution BUF, closes third threeway electromagnetism
Valve V3；
In the present embodiment, the buffer solution BUF can be ammonium chloride buffer solution, and it is molten to be also possible to imidazole buffer
Liquid.Wherein, the volume ratio of the buffer solution BUF and sample solution S that are pumped into the detection device are preferably 1:1.
As a kind of preferred embodiment of the present embodiment, the preferred imidazole buffer solution of buffer solution BUF.Wherein, imidazoles
Concentration be 2.0-5.0g/L, Qula that the volume fraction that 0.5-2.5mL is added in every 1000mL imidazole solution is 50% is logical
The copper-bath of the 2.5g/L of aqueous isopropanol and 0.5-2.5mL form imidazole buffer solution.
As a specific embodiment, the imidazoles of 68.1g can be dissolved in about 900mL deionized water, hydrochloric acid tune pH
Value is to 7.5 and is diluted to 1000mL, obtains imidazole buffer stock solution.Into the imidazole buffer stock solution of 50mL be added 1mL,
The Qula that the copper-bath and 1mL volume fraction of 2.5g/L is 50% leads to aqueous isopropanol, is diluted to 1000mL with distilled water,
The imidazole buffer solution B UF that concentration is 3.4g/L can be obtained.
S404, the second three-way magnetic valve V2 and the 7th three-way magnetic valve V7 is successively opened, forms circulation around circuit, keep imidazoles slow
It rushes solution B UF to be sufficiently mixed with nitrate standard solution, forms uniform solution.
S405, the 4th three-way magnetic valve V4 is opened, the nitrate standard solution that imidazole buffer solution B UF is added is made to flow through cadmium
Circle C is restored, by nitrate reduction at nitrite；
Due to being still at this time circulation patterns, standard solution can be allowed to circulate in the loop repeatedly, carried out multiple
Reduction, to guarantee reduction efficiency.It is to be restored to close the 4th three-way magnetic valve V4 after reaction, close cadmium circle C flow path.
S406, the second three-way magnetic valve V2 and the 7th three-way magnetic valve V7 is closed, disconnects circulation；And it opens the five or three and is powered
Magnet valve V5 after being pumped into a certain amount of first color developing agent SAA, closes the 5th three-way magnetic valve V5；Then, the 6th threeway is opened
Solenoid valve V6 after being pumped into a certain amount of second color developing agent NED, closes the 6th three-way magnetic valve V6；
In the present embodiment, since the liquid in circulation is filled with entire loop, it is necessary to disconnect circulation, suitably discharge
Some sample solution S, could slot milling reception the first color developing agent SAA and the second color developing agent NED.
S407, the second three-way magnetic valve V2 and the 7th three-way magnetic valve V7 is successively opened, forms circulation around circuit, make first to show
Toner SAA and the second color developing agent NED sufficiently develops the color with the standard solution after reduction, forms uniform solution.
S408, the uniform solution in floating cuvette F is irradiated by light source led, and pass through photodiode D acquisition of transmission
Light out, and after being converted into electric signal, output to signal processing system PC obtains transmitted light intensity I1’。
S409, the second three-way magnetic valve V2 and the 7th three-way magnetic valve V7 is successively closed, disconnects circulation, waste liquid W is discharged.So
Afterwards, light source led is closed；Close peristaltic pump P.
S410, formula A=-lg (I is utilized1’/I0') calculate reduction after standard solution in nitrite absorbance,
Obtain the corresponding relationship between the concentration of one group of nitrate and the absorbance of nitrite.
The nitrate standard solution of S411, a variety of various concentrations of selection, repeat step S401-S410, obtain multiple groups
Corresponding relationship between the concentration of nitrate and the absorbance of nitrite is closed with absorbance-concentration that this draws out nitrate
It is curve, the measurement for nitrate content in subsequent sample solution S.
Then, using the absorbance of nitrate-concentration relationship curve, the nitrate in sample solution S to be measured is carried out
Assay, as shown in Figure 5, comprising the following steps:
S501, peristaltic pump P, light source led and the first three-way magnetic valve V1 are opened, is pumped into distilled water DIW and rinses detection device
Flow path.The light transmitted by floating cuvette F is received by photodiode D, is received to signal processing system PC
To after stable signal, current collected light intensity is recorded, incident intensity I is denoted as01'.Close the first three-way magnetic valve V1,
Light source led and peristaltic pump P.
S502, peristaltic pump P and light source led are opened, is pumped into a certain amount of testing sample solution S；
In the present embodiment, the amount of being pumped into of the sample solution S, which is subject to, is full of the flow path that detection device is currently connected to.
S503, third three-way magnetic valve V3 is opened, after being pumped into a certain amount of buffer solution BUF, closes third threeway electromagnetism
Valve V3.
S504, the second three-way magnetic valve V2 and the 7th three-way magnetic valve V7 is successively opened, forms circulation around circuit, keep imidazoles slow
It rushes solution B UF and sample solution S to be sufficiently mixed, forms uniform solution.
S505, open the 4th three-way magnetic valve V4, make be added imidazole buffer solution B UF sample solution S flow through cadmium circle C into
Row reduction, by the nitrate reduction in sample solution S at nitrite；
Due to being still at this time circulation patterns, sample solution S can be allowed to circulate in the loop repeatedly, carried out multiple
Reduction, to guarantee reduction efficiency.Then, the 4th three-way magnetic valve V4 is closed, cadmium circle C flow path is closed.
S506, the second three-way magnetic valve V2 and the 7th three-way magnetic valve V7 is closed, disconnects circulation；And it opens the five or three and is powered
Magnet valve V5 after being pumped into a certain amount of first color developing agent SAA, closes the 5th three-way magnetic valve V5；Then, the 6th threeway is opened
Solenoid valve V6 after being pumped into a certain amount of second color developing agent NED, closes the 6th three-way magnetic valve V6.
S507, the second three-way magnetic valve V2 and the 7th three-way magnetic valve V7 is successively opened, forms circulation around circuit, make first to show
Toner SAA and the second color developing agent NED sufficiently develops the color with the sample solution S after reduction, forms uniform solution.
S508, the uniform solution in floating cuvette F is irradiated by light source led, and pass through photodiode D acquisition of transmission
Light out, and after being converted into electric signal, output to signal processing system PC obtains transmitted light intensity I11’。
S509, the second three-way magnetic valve V2 and the 7th three-way magnetic valve V7 is successively closed, disconnects circulation, waste liquid W is discharged.
S510, third three-way magnetic valve V3 and the 4th three-way magnetic valve V4 is opened, imidazole buffer solution B UF is made to be filled into cadmium
It encloses in C, to protect cadmium circle C.Then, light source led is closed；Close peristaltic pump P.
S511, formula A=-lg (I is utilized11’/I01') calculate reduction after sample solution S in nitrite suction
Luminosity, it is then molten according to calculated absorbance and the absorbance of nitrate-concentration relationship curve, the sample after being restored
The content of nitrate, is denoted as CNO in liquid S3 _-N'.Due to the nitrate content CNO calculated at this time3 -- N ' is sample to be tested
The total content of nitrite and nitrate in solution S, therefore, the actual content CNO of nitrate in sample solution S3 -- N=
CNO3 --N’-CNO2 _-N。
The measurement to nitrate content in sample to be tested solution S is just completed as a result,.
The detection device of the present embodiment is designed using circulation, and reaction efficiency greatly improves, and the reaction in entire loop generates
Object concentration is uniform, therefore can repeatedly measure averaged, to improve the collimation and stability of testing result.
In the present embodiment, cadmium circle C needs to clean and activate when using for the first time, when the reduction efficiency of cadmium circle C drops to
It when 90% or less, should activate, can just continue to use again.
Following steps can be used to the cleaning of cadmium circle C:
Distilled water is extracted with the syringe of 25mL to clean for several times cadmium circle C；Then the nitric acid for extracting 2mL, 2mol/L is quick
It rinses；It is alternately rinsed with 20mL concentrated hydrochloric acid and 20mL distilled water again；Finally distilled water flushing is extracted again for several times.
Following steps can be used to the activation of cadmium circle C:
Cadmium circle C is accessed into flow path, peristaltic pump P is opened, the hydrochloric acid of 2mol/L is pumped into from the channel imidazole buffer solution B UF, and
Continue 1 minute；It is then pumped into copper activating fluid, and continues 2 minutes；It is pumped into the hydrochloric acid of 2mol/L again, and continues 5 minutes；Finally pump
Enter imidazole buffer solution B UF, completes the activation to cadmium circle C.Certainly, the process can also be by removing cadmium circle C using injection
Device is completed.
Certainly, the above is only a kind of preferred embodiment of the invention, it is noted that for the general of the art
For logical technical staff, various improvements and modifications may be made without departing from the principle of the present invention, these improve and
Retouching also should be regarded as protection scope of the present invention.
Claims (3)
1. a kind of nitrate content detection method is applied in nitrate content detection device, the nitrate content detection dress
It sets and includes:
First three-way magnetic valve, normal open entrance is for receiving sample solution to be detected, and normally closed entrance is for receiving distillation
Water；
Second three-way magnetic valve, normal open entrance are connected to the outlet of the first three-way magnetic valve；
Third three-way magnetic valve, normal open entrance are connected to the outlet of the second three-way magnetic valve, and normally closed entrance is for receiving buffering
Solution；
4th three-way magnetic valve, normal open entrance are connected to the outlet of third three-way magnetic valve, and normally closed entrance is connected to by cadmium circle
The outlet of the third three-way magnetic valve；
5th three-way magnetic valve, normal open entrance are connected to the outlet of the 4th three-way magnetic valve, and normally closed entrance is for receiving first
Color developing agent；
6th three-way magnetic valve, normal open entrance are connected to the outlet of the 5th three-way magnetic valve, and normally closed entrance is for receiving second
Color developing agent；
Peristaltic pump, entrance are connected to the outlet of the 6th three-way magnetic valve；
Floating cuvette, entrance are connected to the outlet of peristaltic pump, optical entrance are provided on the floating cuvette and light goes out
Loophole；
Light source, the optical entrance of floating cuvette described in face, the liquid in transmitting light irradiation floating cuvette；
Optical receiver, the optical emission exit of floating cuvette described in face receive the light projected by optical emission exit, and
It is converted into electric signal, output to signal processing system；
7th three-way magnetic valve, entrance are connected to the outlet of floating cuvette, normal open outlet for being discharged waste liquid, it is normally closed go out
The normally closed entrance of mouth the second three-way magnetic valve of connection；
It is characterized in that, detection method includes the following steps for the nitrate content:
A, peristaltic pump, light source and the first three-way magnetic valve are opened, is pumped into the flow path of detection device described in distilled water flushing, and pass through
Optical receiver acquires incident intensity I0；
B, the first three-way magnetic valve described in closing, is exported to switch to and is connected to its normal open entrance, and known concentration is pumped into
Nitrite standard solution；
C, the 5th three-way magnetic valve is opened, after being pumped into a certain amount of first color developing agent, closes the 5th three-way magnetic valve；It opens
6th three-way magnetic valve after being pumped into a certain amount of second color developing agent, closes the 6th three-way magnetic valve；
D, the second three-way magnetic valve and the 7th three-way magnetic valve are opened and form closed loop flow path, make the nitrite standard solution with
First color developing agent and the second color developing agent are formed by mixed liquor abundant reaction solution in circulation；
E, the mixed liquor in the light source irradiation floating cuvette is opened；
F, pass through the optical receiver acquisition of transmission light intensity I1, by formula A=- lg(I1/I0) calculate the standard solution Central Asia
The absorbance of nitrate；
G, second three-way magnetic valve and the 7th three-way magnetic valve are closed, waste liquid is discharged；
H, the nitrite standard solution for replacing various concentration, repeats the step a-g, draws out the extinction of nitrite
Degree-concentration relationship curve；
I, nitrite standard solution is substituted for sample solution to be measured, repeats step a-g, according to calculated sample
The absorbance of nitrite in solution and the absorbance of the nitrite-concentration relationship curve, it is molten to obtain the sample
The content CNO of nitrite in liquid2 --N；
J, absorbance-concentration relationship curve of nitrate is drawn, comprising the following steps:
(1) peristaltic pump, light source and the first three-way magnetic valve are opened, is pumped into the flow path of detection device described in distilled water flushing, and lead to
Cross optical receiver acquisition incident intensity I0'；
(2) first three-way magnetic valve is closed, is exported to switch to and is connected to its normal open entrance, known concentration is pumped into
Nitrate standard solution；
(3) third three-way magnetic valve is opened, a certain amount of buffer solution is pumped into, is then turned on the second three-way magnetic valve and the seven or three
Three-way electromagnetic valve forms circulation around circuit, and buffer solution and nitrate standard solution is made to be thoroughly mixed to form uniform solution；
(4) the 4th three-way magnetic valve is opened, so that the nitrate standard solution that buffer solution is added is flowed through cadmium circle and is repeatedly restored,
By the nitrate reduction in the standard solution at nitrite；
(5) the 5th three-way magnetic valve is opened, after being pumped into a certain amount of first color developing agent, closes the 5th three-way magnetic valve；It opens
The 6th three-way magnetic valve is opened, after being pumped into a certain amount of second color developing agent, closes the 6th three-way magnetic valve；
(6) it opens the second three-way magnetic valve and the 7th three-way magnetic valve forms closed loop flow path, keep the uniform solution aobvious with first
Toner and the second color developing agent are formed by mixed liquor abundant reaction solution in circulation；
(7) mixed liquor in the light source irradiation floating cuvette is opened；
(8) pass through the optical receiver acquisition of transmission light intensity I1', by formula A=- lg(I1’/I0') calculate the standard after reduction
The absorbance of nitrite in solution；
(9) second three-way magnetic valve and the 7th three-way magnetic valve are closed, waste liquid is discharged；
(10) the nitrate standard solution for replacing various concentration, repeats step (1)-(9), obtains the suction of multiple groups nitrite
The corresponding relationship of luminosity and nitrate concentration draws out absorbance-concentration relationship curve of nitrate with this；
K, nitrate standard solution is substituted for the sample solution to be measured, repeats the step (1)-(9), calculates
Then the absorbance of nitrite in sample solution after reduction utilizes absorbance-concentration relationship curve of the nitrate, obtains
Obtain the content summation CNO of NO3-N and NO2-N in the sample solution3 --N'；
L, the nitrate content CNO in the sample solution is calculated3 --N=CNO3 --N’-CNO2 --N。
2. nitrate content detection method according to claim 1, which is characterized in that
The buffer solution is ammonium chloride buffer solution or imidazole buffer solution, wherein is pumped into the detection device
The volume ratio of buffer solution and sample solution is 1:1；
First color developing agent is P-aminobenzene-sulfonamide-aqueous hydrochloric acid solution, wherein the concentration of P-aminobenzene-sulfonamide is 5-
30g/L, the concentration of hydrochloric acid are 1-2mol/L, and the volume for the first color developing agent and sample solution being pumped into the detection device
Than for 1:50；
The second color developing agent NED is hydrochloride naphthodiamide aqueous solution, wherein the concentration of hydrochloride naphthodiamide is 1.0-5.0g/
L, and the volume ratio for the second color developing agent and sample solution being pumped into the detection device is 1:50.
3. nitrate content detection method according to claim 1 or 2, which is characterized in that imitated in the reduction of the cadmium circle
When rate drops to 90% or less, the cadmium circle is activated again, the steps include:
The peristaltic pump, third three-way magnetic valve and the 4th three-way magnetic valve are opened, the hydrochloric acid of 2mol/L is pumped into, and continues 1 point
Clock；It is then pumped into copper activating fluid, and continues 2 minutes；It is pumped into the hydrochloric acid of 2mol/L again, and continues 5 minutes；Finally, being pumped into described
Buffer solution.
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| CN109142220A (en) * | 2018-08-31 | 2019-01-04 | 青岛卓建海洋装备科技有限公司 | Seawater Nitrate/nitrite on-line analysis |
| CN109541248B (en) * | 2018-12-11 | 2023-09-15 | 苏州英赛斯智能科技有限公司 | Flow injection reaction tank device and reversing fluid unit for same |
| CN109932230A (en) * | 2019-03-29 | 2019-06-25 | 广东省生物工程研究所（广州甘蔗糖业研究所） | A kind of nitrate reduction instrument and its application method |
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